CN1788025A - Dosing of peroxide to a suspension process wherein styrene is polymerized - Google Patents

Dosing of peroxide to a suspension process wherein styrene is polymerized Download PDF

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CN1788025A
CN1788025A CNA2004800129074A CN200480012907A CN1788025A CN 1788025 A CN1788025 A CN 1788025A CN A2004800129074 A CNA2004800129074 A CN A2004800129074A CN 200480012907 A CN200480012907 A CN 200480012907A CN 1788025 A CN1788025 A CN 1788025A
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initiator
polymerization
weight
monomer
metered charge
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CN100439406C (en
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H·G·贝维布林克
F-J·霍格斯特格尔
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Nouryon Chemicals International BV
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Akzo Nobel NV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

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Abstract

The invention relates to a suspension polymerization process for the preparation of styrene-containing (co)polymers, wherein the process comprises the steps of continuously or semi-continuously dosing an initiator to the reaction mixture, said initiator having a specified half-life at the temperature of the reaction mixture to which it is dosed. The invention further relates to styrene based (co)polymer obtainable by said process, and to the use of said styrene (co)polymer in a shaping process.

Description

Metered charge superoxide in the suspension process of styrene polymerization
The present invention relates to a kind of in suspension polymerizing styrene monomer or contain cinnamic monomer mixture and prepare the discontinuous method that is substantially free of vinylchlorid that contains cinnamic (being total to) polymkeric substance, wherein this method is included under the polymerization temperature continuously or the step of metered charge initiator in polyblend semi-continuously.The invention still further relates to styryl (being total to) polymkeric substance that can obtain by described method, and the application of described vinylbenzene (being total to) polymkeric substance in forming method.
Being used for the polymerizing styrene monomer methods is known in this area, for example referring to US4, and 363,881 and US6,153,658.Here described a kind of traditional method, wherein in the intermittence suspension process, added superoxide at two points, but wherein said superoxide metered charge not.US5,189,069 suggestion metered charge are dissolved in initiator in the monomer to obtain the styrene beads of grain-size controlled.The transformation period of conventional initiator under the metered charge temperature of using was above one hour.In EP-A-0234705 and EP-A-0488025, disclose similar method, wherein used different technology, promptly begun the polymerization species grain of " under planting " significant quantity in reaction mixture before the initiator solution continuous charging is in the monomer.In addition, in EP-A-0234705, the transformation period of the initiator of metered charge under the metered charge temperature was above one hour.US5,905,096 have described the another kind of method for preparing polystyrene suspension.Form the prepolymer that contains superoxide and whipping agent this moment, and it is suspended subsequently and reacts to end.All these method purposes all are control size, but their shortcoming be, if possible, be difficult to pre-determine the molecular weight and the controlled polymerization speed of described polymkeric substance.In addition, the polymerization time that these methods need be grown and generally include more than one reactions steps, and initiator often adds with the solution form that is in the monomer, and this undesirable (in advance) polymerization can occur before it joins in the described reactor, therefore, may be unsafe.
The purpose of this invention is to provide a kind of polymerizing styrene monomer methods that is used to prepare styryl (being total to) polymkeric substance (being also referred to as " polystyrene " in this manual), this method can be controlled molecular weight and molecular weight distribution well, thereby obtain can with the polymkeric substance of the polymer phase ratio of traditional method, but only need short polymerization time.Use at least a initiator in the method, this initiator when satisfying requirement of the present invention all or part of be measured reinforced.More particularly, the selection of the described at least a reinforced initiator that is measured should make the requirement of satisfying the transformation period under the design of given polymerization temperature.The application hereinafter this initiator be called " described initiator ".The present invention also comprises such method, the wherein combination of metered charge initiator, and condition is that the combination of this initiator contains " described initiator ".It should be noted that term " initiator " has comprised such initiator combination from this point.Should also be noted that " described initiator " can be used in combination with other initiator.In this case, latter's metered charge or only be added into and be not measured reinforced separately.
In the methods of the invention, can control the molecular weight and the molecular weight distribution of polystyrene in the styrene monomer polymerization process, the overall space-time yield of polymerization unit is improved simultaneously.
Should be noted that this method does not need to use prepolymerization technology or adds kind of a grain.But if desired, polymer beads particularly can recirculation by the particle with undesirable granularity of the polymerization batches generation of morning.If you are using, surpassing 50% particle preferably is dissolved in the monomer in reaction mixture is heated to the process of polymerization temperature.
Be also noted that WO 00/17245 discloses a kind of method, wherein vinylchlorid can have copolymerization in the suspension process of superoxide in metered charge with vinylbenzene.Present method is different from the method for WO 00/17245, and difference is that present method is substantially free of vinylchlorid, refers to that promptly the amount of vinylchlorid is lower than 1 weight % in whole monomeric weight, preferably is lower than 0.1 weight %.Preferably, vinyl-chloride-containing not fully in present method process is to avoid in this procedure pressure to increase and to avoid environmental problem.As known in the art, it is different greatly that the polymerization kinetics of chloroethylene polymerization and the kinetics of other ethylenically unsaturated monomer have, because the chain transfer that participates in the polymerization process of vinyl-chloride-containing in the monomer reaction is dominant.The main difference part that this causes is that the molecular weight of vinyl chloride-base polymer depends on polymerization temperature greatly, and situation is not like this when forming polystyrene.
In the metered charge process of initiator, will form polymerisate.Therefore, after for some time with the initiator metered charge to the mixture of monomer and polymerisate.Preferably, with initiator at least 0.5 hour, more preferably at least 1 hour during in metered charge continuously or semi-continuously.When preparing number of polymers with intermittent mode, molecular weight as required, the reinforced time may as many as 5 hours or more.From industry and technical standpoint, the reinforced more semi-continuous metered charge of the continuous measurement of initiator is more preferred.
Preferably, in polyblend the metered charge initiator at least 20%, preferably at least 40%, more preferably at least 70% monomer generation polymeric semi-continuously or continuously carried out in the time period.If the selection semi continuous operation has a plurality of (preferred 4 or the more a plurality of) period under the polymerization temperature of metered charge small portion initiator.If wish like this, semicontinuous and operate continuously just can merge, thus in certain period (length or shorter) metered charge initiator repeatedly.
Most preferably, continuous or the semicontinuous metered charge of initiator is from least 1%, preferably at least 0.5%, more preferably at least 0.1%, most preferably there is not monomer generation polymeric time point to begin up at least 70%, preferably at least 80%, more preferably at least 90% monomer, most preferred monomer all takes place till the polymerization basically." polymerization all taking place basically " refers to exist in final polymerisate the monomer that is lower than 1000ppm.
Term " continuously " also comprises with variable speed and variable timed interval continuous charging.Add initiator for the cooling power of utilizing polyreaction with optimum way with prevent that so-called in the polymerization process " out of control " is good with variable speed.Term " semicontinuous " refers to the initiator of a plurality of parts wherein and joins charging process in the polyblend.If in short interval, add a plurality of part initiators, then approach the continuous charging method.
In one embodiment, the inventive method relates to the polymerization that also comprises the mixture that contains styrene monomer of comonomer in addition.In this embodiment, preferably contain cinnamic monomer mixture and contain vinylbenzene in whole monomeric weight at least 50 weight %.Operable comonomer is general type, and is preferably selected from vinyl acetate, ethene, and propylene, vinyl cyanide, divinyl and (methyl) acrylate, and comprise the olefinic unsaturated polymer, as polyhutadiene and styrene-butadiene rubber(SBR).Although not too preferred, also can with the vinylidene chloride copolymerization.More preferably, at least 80 weight % are vinylbenzene in the monomer that is aggregated, and most preferred method is that whole basically monomers all are cinnamic methods.
In the methods of the invention, require to make the described initiator can be when under polymerization temperature, be present in the reaction mixture for transformation period of initiator in decomposition 50% or more (based on molar weights) in 60 minutes or the shorter time.Preferably, the transformation period under polymerization temperature in reaction mixture is less than 50 minutes, more preferably less than 40 minutes, even more preferably less than 30 minutes, most preferably is less than 15 minutes.Simultaneously, the transformation period under polymerization temperature in reaction mixture surpasses 0.5 minute, more preferably surpasses 1 minute, even more preferably surpasses 2.5 minutes, most preferably above 5 minutes.The minimum transformation period is 0.5 minute or more, otherwise initiator will be invalid.It is believed that described under the shorter transformation period be invalid be because such fact: before initiator was decomposing, initiator should pass reaction mixture if having time and migrate to the polymer/monomer phase, and this two-phase is discontinuous mutually.Because redox initiation system almost forms free radical in moment usually, therefore, such initiator system is not too preferred equally.
Surprisingly, we find, the combination that traditional styrene suspension polymerization process can be by utilizing the metered charge technology and select suitable initiator to improve.Only use traditional superoxide and make it decompose the polymkeric substance that will obtain the molecular-weight average reduction quickly by improving polymerization temperature.Only the superoxide that metered charge is traditional will cause polymerization time to slow down, rather than faster.But, the combination of these two measures, promptly these two combines and then can make obtain product like molecular-weight average and the traditional product type in the polymerization time that shortens the faster decomposition of superoxide with its metered charge.
Preferably, polymerization temperature is at most 170 ℃.Preferably, temperature of reaction is 150 ℃ or lower, more preferably 130 ℃ or lower.
The transformation period of all initiators that use all can be measured by traditional Study of Thermal Decomposition in monochloro benzene, as known in the art (referring to for example Akzo Nobel, be numbered 10737 brief introduction material, " Initiators for high polymers (superpolymer initiator) ").
By using one or more other initiators, we find, compare with the traditional method that difference is not to be measured initiator reinforced and metered charge method do not give optimization, can realize same or lower monomer residue concentration.Therefore, the preferred not only described initiator of metered charge but also use one or more other initiators.If this other initiator is used for present method, in them each transformation period in reaction mixture under polymerization temperature preferably is less than 120 minutes, more preferably less than 60 minutes, even more preferably less than 30 minutes, most preferably be less than 10 minutes, and preferably surpass 0.05 minute, more preferably above 0.5 minute, even more preferably surpass 2.5 minutes, most preferably above 5 minutes.Described one or more other initiators are disposable join in the polyblend or metered charge in polyblend.
Preferably, the initiator of all metered charge all satisfies described transformation period requirement basically.More preferably, the initiator of the present method that is useful on all satisfies described transformation period requirement basically.
Notice that term " initiator " is used for herein with its classical sense, produce the compound of the free radical of initiated polymerization subsequently to be used to refer to those.Therefore, when under polymerizing condition (all or part of) remain, for example like this they will be present in the final polymkeric substance when using some heat-labile compound as the fire retardant synergist, and Undec part just is not counted as according to initiator of the present invention.
Can being measured, the described transformation period reinforced and that satisfy initiator, to require the example of initiator of the suitable type of (depending on actual polymerization temperature) be peroxy dicarbonate; peroxycarbonates; peroxyester; peroxy ketal; diacyl peroxide; dialkyl peroxide, azo initiator, ketone peroxide and composition thereof.These initiator per molecules can contain one or more peroxides and/or azo segment.Optional is, these initiators are also by one or more functional groups, and for example amine, phosphate radical, ester, ether and/or alcohol radical are further functionalized.Still making polymkeric substance have common molecular weight when can farthest reduce polymerization time is found and is applicable to such product, this product is selected from has dibenzoyl peroxide segment or 1, pulsating superoxide of 1-two (tert-butyl hydroperoxide) hexanaphthene and azo initiator.
Having pulsating preferred compound of benzoyl peroxide and a transformation period thereof lists in the table 1.
Table 1
Figure A20048001290700081
In last table, T10 be when the transformation period of compound being 10 hours temperature (℃), T1 be when the transformation period of compound being 1 hour temperature (℃), Ea is an activation energy, unit is J/mol, and A is the Arrhenius frequency factor, unit is s -1Use traditional arrhenius equation, can calculate the transformation period under the polymerization temperature.
More preferably replace or unsubstituted dibenzoyl peroxide, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexane, 2,2-two (tert-butyl hydroperoxide) butane, 1,1-two (tert-butyl hydroperoxide) hexanaphthene and azo initiator.Dibenzoyl peroxide most preferably, 1,1-two (tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane, 2,2 '-azo two (isopropyl cyanide) and 2,2 '-azo two (2-methylbutyronitrile).Commercially available initiator can obtain with following listed trade(brand)name: as Trigonox 99, Trigonox SBP, Trigonox EHP, Trigonox 131, Trigonox 141, Trigonox 21S, Perkadox 16, Trigonox 27, Trigonox 22, Trigonox 29, Trigonox 25, Trigonox 125, Trigonox 121, Trigonox 421, Trigonox 425, Perkadox AMBN, Perkadox AIBN, Perkadox LW-75, Perkadox 12 and Laurox.
The other initiator that is used for present method is different from described initiator, but can be selected from compound on the same group.
If hot start method is prepared-be called to reaction mixture at polymerization temperature or near under the polymerization temperature, then do not require before reaction mixture reaches temperature of reaction, to add a certain amount of initiator and metered charge residue initiator under temperature of reaction.But, in hot start method, being no more than 10 weight % in monomeric combination weight equally in disposable in reaction mixture, the adding before the polymerization, the initiator that preferably is no more than 5 weight % may be useful.Then can be under temperature of reaction the described initiator of metered charge continuously or semi-continuously.If this program of use then after monomer, solvent and other possible component have been mixed, adds first initiator as last composition.If in reaction mixture, there is a certain amount of polymerization retarder (catching the species of free radical), then preferred especially this program.If there is such free-radical scavengers, for example because it is included in the monomer as monomer component (adds as stablizer) usually, the initiator of so initial metered charge will react with described scavenging agent, thereby prevent the start delay of polyreaction.
Preferably, the type of other initiator and the selection of amount should make in the final polymerisate monomer residual volume less than 5, the 000mg/kg monomer, and preferably less than 2, the 000mg/kg monomer, more preferably less than 1, the 000mg/kg monomer.
The total amount that is used for the initiator of the inventive method is being generally used within the scope of polymerization process.Usually preferably, to treat the weight of polymerization single polymerization monomer, use the 0.01 weight % that is at least of all amount of initiator, more preferably at least 0.05 weight %, at least 0.1 weight % most preferably, and preferred 5 weight % at the most, more preferably 3 weight % at the most, most preferably 1 weight % at the most.
Metered charge is carried out usually as follows in reactor: metered charge initiator itself (pure), as with the mixture or the solution form metered charge of one or more solvents, or carry out metered charge as dispersion liquid.The solvent that is fit to is preferably selected from water, traditional organic solvent, monomer, whipping agent (as pentane, iso-pentane etc.) and composition thereof.For the reason of safety or quality control, may preferred and monomeric mixture.The preferred dispersion liquid that uses initiator, more preferably aqueous dispersions.Most preferably use the suspension of initiator in water, as the dibenzoyl peroxide aqeous suspension of 40 weight %.Described suspension can be the commodity Perkadox by name that derives from Akzo Nobel Polymer Chemicals The commercially available prod of LW-40.If use solvent such as alcohol, then they can be removed in the last handling process of polymkeric substance after polymerization process.If you are using, advantageously, use the solvent that can not cause disadvantageous effect to the thermostability that is dissolved in initiator wherein, this can obtain confirming by analyzing the half life temperature (temperature when transformation period be 1 hour) of initiator in described solvent.An example of the solvent that can use with most of initiators is a Permethyl 99A..If the dispersion liquid of metered charge initiator, then this dispersion liquid can be the dispersion liquid of initiator self, or the dispersion liquid of the solution of described initiator.Preferably, described dispersion liquid is an aqueous dispersions.Preferably, use the initiator solution or the dispersion liquid of dilution, guaranteeing the short mix of initiator and polyblend, thereby make the utilization of initiator more abundant.Therefore, the preferred initiator concentration that uses is at least 0.1 weight %, more preferably at least 0.5 weight %, most preferably at least 2 weight % and maximum 60 weight %, more preferably maximum 25 weight %, the mixture of the initiator of most preferably maximum 15 weight %, solution or dispersion liquid.
Described polymerization process is a suspension process, and wherein reaction mixture is to contain the dispersion liquid of monomer in water-bearing media.In these methods, can use additive commonly used.For example,, can there be one or more typical additives such as tensio-active agent, chain-transfer agent, protective colloid, stain control agent, pH buffer reagent, fire retardant, flame retardancy synergists etc. for aqeous suspension.Whipping agent can add when polymerization process begins or in the process of carrying out.Owing to have styrene monomer and whipping agent, therefore, this method is at least partially in carrying out in the pressurized reactor.The combination weight of additive is preferably maximum 20 weight % in all monomeric combination weights.
Because present method has the polymerization time of shortening, therefore,, preferably add whipping agent in the stage more Zao than traditional method if use whipping agent.More preferably, partly or entirely whipping agent,, most preferably was incorporated in the reaction mixture less than 50% o'clock preferably less than 60% less than 80% in the monomer polymerization degree.The method that is fit to finds it is metered charge or add the method for whipping agent in after polymerization begins one hour.The most preferred method of the present invention is to be used to prepare the suspension polymerization at intermittence that uses whipping agent comprising of expandable polystyrene (EPS) (EPS).
Utilize this fact of cooling power of polyreaction in the mode of optimum except helping with variable speed metered charge initiator, find that also changing metered charge speed in the polymerization process process is useful for obtaining economic polymerization process and obtaining to have the polymerisate of wishing molecular weight.Has the polymkeric substance that multimodal molecular weight distributes by in a batch of process, changing metered charge speed, can preparing.For example, distribute by in two periods, using different metered charge speed can in same batch, produce bimodal molecular weight.This have a high molecular part that polymeric blends that bimodal molecular weight distributes has the low molecular weight part of the expandability that can be used for improving polystyrene and can be used for improving the polymer machinery performance.
Also find in addition, can prepare the molecular weight polymkeric substance substantially the same with the traditional method resulting polymers with the short time, only difference is that controlled metered charge initiator and optimization are used for the initiator of metered charge method.
After the polymerization, gained (being total to) polymkeric substance (or resin) is preferably handled in the common mode in this area.The polymkeric substance that obtains like this can carry out common monomer minimizing, dry and/or screening step.After these one or more steps, can carry out for example foaming step.As in traditional EPS method, available common mode reduces the content of residual monomer in the polymerisate; Preferably by introducing second step in the method, temperature of reaction is higher than the temperature that initiator is measured and uses in the reinforced the first step in this second step, usually approximately be 110-170 ℃, and preferably there is one or more half life temperatures other initiator as defined above, as peroxidized t-butyl perbenzoate, t-butyl peroxy-2-ethylhexyl carbonic ether, dicumyl peroxide or tert-pentyl peroxide-2-ethylhexyl carbonic ether.These other initiators can add when polymerization process begins or in the process of carrying out.The gained resin is characterised in that, at 60 ℃ down after dry 1 hour and the screening, it preferably contains less than 50ppm, more preferably less than 40ppm, most preferably less than the residual initiator of 25ppm.
The gained resin is further characterized in that its weight-average molecular weight (Mw) preferably is at least 100,000g/mol, more preferably at least 125,000g/mol, most preferably at least 150,000g/mol and its Mw preferably are at most 500,000g/mol, more preferably at the most 450,000g/mol, most preferably at the most 350,000g/mol, described Mw use polystyrene as standard test according to traditional gel permeation chromatography technology.
The invention still further relates to styryl (being total to) polymkeric substance that can obtain by aforesaid method, and this vinylbenzene (being total to) polymkeric substance is comprising with this (being total to) polymkeric substance heating with the application in the forming method of preparation foaming product.
The present invention will be described by following indefiniteness embodiment.
Embodiment 1-4 and comparative example A-D
The general introduction of experiment 1-4 and A-D:
BPO, PxL (Perkadox LW-75) dibenzoyl peroxide (initiator), AkzoNobel produces.
Tx-117 (Trigonox 117) t-butyl peroxy 2-ethylhexyl carbonic ether (other initiator), Akzo Nobel produces.
Tx-131 (Trigonox 131) tert-pentyl peroxide 2-ethylhexyl carbonic ether (other initiator), Akzo Nobel produces.
In 1 liter of stainless steel B ü chi reactor of the temperature control that baffle plate, three leaf agitators, pressure transmitter, initiator metered charge pipeline and nitrogen purging device are housed, add 1.25 gram tricalcium phosphates.Add 230 gram water then, the Nacconol of 20 grams, 0.1 weight % The Gohsenol of 90G (the Stephan Chemie Co. product) aqueous solution and 10 grams, 0.5 weight % The solution of C500 (the Nippon Gohsei product) aqueous solution and stir about 5 minutes.In this reactor, add the 220g styrene monomer.Reactor is vacuumized several times to remove deoxidation, adds nitrogen and protect, the off-response device, pressurization, and at 45 minutes internal heating to polymerization temperature.For comparative example A-D, polymerization temperature is 90 ℃.After keeping 255 minutes under 90 ℃, temperature was risen to 120 ℃ in 60 minutes.This temperature kept 120 minutes.Then, whole system is cooled to room temperature.
In embodiment 1-4, under 110 ℃ polymerization temperature, carry out the metered charge of initiator by pressure pump.In the embodiment that does not use pentane, with Perkadox LW-75 is with the solution form metered charge in 90 minutes in 30 gram vinylbenzene.After 190 minutes, in 15 minutes, other initiator is added with the solution form in 5 gram vinylbenzene.In the embodiment that uses pentane, add BPO with the solution form in vinylbenzene and pentane (30 grams/15 grams), and other initiator adds in 15 minutes with the solution form in 5 gram pentanes after 190 minutes polymerization time.In all embodiment 1-4, after 190 minutes, temperature was increased to 120 ℃ in 30 minutes in polymerization under 110 ℃ the temperature.This temperature kept 80 minutes.Then, with the content cool to room temperature of reactor.
The results are shown in following table.As can be seen, by metered charge initiator (embodiment 1-4), can obtain its molecular-weight average (Mw and Mn) and polymolecularity and the initiator therein embodiment that metered charge and temperature the are not lower (EPS that comparative example A-D) is identical.In the metered charge experiment of not using pentane (embodiment 3-4), obtained the low residue vinylbenzene value identical equally with the non-metering reinforced experiment (Comparative Examples C-D) of wherein not using pentane.
Embodiment 1 2 3 4 A B C D
Add pentane Do not add pentane Add pentane Do not add pentane
Other initiator Tx-117 Tx-131 Tx-117 Tx-131 Tx-117 Tx-131 Tx-117 Tx-131
Mw product (* 1000) g/mol 221 191 265 260 243 195 275 251
Mn product (* 1000) g/mol 79 72 85 84 85 78 101 87
D(Mw/Mn) 2.8 2.6 3.1 3.1 2.9 2.5 2.7 2.9
Vinylbenzene residual (weight %) 1.76 4.14 0.17 0.28 0.75 0.66 0.31 0.19
Polymerization time 300 300 300 300 480 480 480 480
BPO measures (meq/100g vinylbenzene) 1.24 1.24 1.24 1.24 0.98 0.98 0.98 0.98
The BPO metered charge time (min) 90 90 90 90 0 0 0 0
Other amount of initiator (meq/100g vinylbenzene) 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46
The metered charge time (min) of other initiator 15 15 15 15 0 0 0 0
Kick off temperature (℃) 110 110 110 110 90 90 90 90
The highest polymerization temperature (℃) 120 120 120 120 120 120 120 120
Embodiment 5-9 and Comparative Examples E:
Px-BC (Perkadox BC-FF) dicumyl peroxide, Akzo Nobel produces
Repeat the previous embodiment program, difference is to add 260 gram water.In embodiment 5,8 and 9, other initiator 180,160 and 135 minutes after the reaction beginning respectively is added in the polyreaction.In embodiment 6,7 and E, other initiator is disposable adding before polymerization begins.
In embodiment 5 and 8, be 110 ℃ of following polymerizations after 190 minutes, 15 minutes (embodiment 5) or in (embodiment 8) temperature was risen to 120 ℃ in 30 minutes.This temperature keeps 50 minutes (embodiment 5) or 80 minutes (embodiment 8).
In embodiment 7, be that 110 ℃ of following polymerizations after 175 minutes, rose to 130 ℃ with temperature in 60 minutes.This temperature kept 100 minutes.In embodiment 6, be that 110 ℃ of following polymerizations after 155 minutes, rose to 120 ℃ with temperature in 30 minutes.This temperature kept 65 minutes, in 15 minutes temperature was risen to 150 ℃ then, and this temperature kept 95 minutes.
The results are shown in following table.As can be seen, aspect molecular weight and molecular weight distribution, the polystyrene that obtains in polymerization process of the present invention is with suitable with the polystyrene of traditional method gained, but the polymerization time that the inventive method needs is shorter.
(contrast) embodiment 5 6 7 8 9 E
Initiator Px-L W75 Px-L W75 Px-L W75 Px-L W40 Px-L W40 Px-L W75
Other initiator Tx-131 Tx-117 Tx-BC Tx-131 Tx-131 Tx-117
Mw product (* 1000) g/mol 260 229 231 284 279 243
Mn product (* 1000) g/mol 84 75 72 92 102 101
D(Mw/Mn) 3.1 3.1 3.2 3.1 2.8 2.7
Vinylbenzene residual (weight %) 0.28 0.10 0.50 0.17 0.07 0.31
Polymerization time 300 370 325 300 300 480
BPO measures (meq/100g vinylbenzene) 1.24 0.83 1.53 1.24 0.98 0.98
The BPO metered charge time (min) 90 90 90 75 80 0
Other amount of initiator (meq/100g vinylbenzene) 0.46 0.87 0.46 0.46 0.46 0.46
The metered charge time (min) of other initiator 15 0 0 5 5 0
Kick off temperature (℃) 110 110 110 110 110 90
The highest polymerization temperature (℃) 120 150 130 120 120 120
Embodiment 10-11
PxL W40 (Perkadox -L W40-TCP) dibenzoyl peroxide suspension, AkzoNobel produces
Repeat the program of embodiment 5, difference is not use other initiator.In embodiment 10, use PxL W40.Superoxide suspension is with the form of suspension metered charge (in 30 gram water, the injection rate of water is calibrated according to this amount during the reaction beginning) of dilution.In embodiment 11, use Perkadox L W-75, and with the solution form metered charge in 30 gram vinylbenzene.The temperature of essential control styrene solution is in order to avoid polymerization takes place in solution self.
The result is as follows:
Embodiment 10 Embodiment 11
Transformation efficiency (%) 99.0 83
Monomer residue (%) 1.02 17
Mw 245000 185000
Mn 88000 70000
Dispersed 2.8 2.6
As can be seen, for the inventive method, use BPO suspension to use BPO solution more preferred.

Claims (13)

1. suspension polymerization of essentially no vinylchlorid that is used for the polymerizing styrene monomer or contains the mixture of styrene monomer, it is included in the polymerization temperature downhill reaction mixture continuously or the step of metered charge initiator or initiator mixture semi-continuously, it is characterized in that the transformation period of at least a initiator under described polymerization temperature of metered charge is 60 minutes or shorter.
2. according to the process of claim 1 wherein that composition further comprises the comonomer that is selected from vinyl acetate, ethene, propylene, vinyl cyanide, divinyl, (methyl) acrylate and olefinic unsaturated polymer such as polyhutadiene and styrene-butadiene rubber(SBR).
3. according to the method for claim 1 or 2, wherein with described initiator continuously or semi-continuously from least 1%, preferably at least 0.5%, more preferably at least 0.1%, most preferably there is not monomer generation polymeric time point to begin up at least 70%, preferably at least 80%, more preferably at least 90%, most preferably basically all monomers metered charge till the polymerization all takes place, wherein term " all polymerization all takes place monomers basically " refers to have less than 1 the monomer of 000ppm in final polymerisate.
4. according to any one method of claim 1-3; wherein said initiator is selected from peroxy dicarbonate; peroxycarbonates; peroxyester; peroxy ketal; diacyl peroxide; dialkyl peroxide, ketone peroxide, azo initiator and its mixture; in these initiators each all can have one in per molecule; two or more-OO-and/or-the NN-segment; and each in these initiators is also optional by amine; phosphate radical; ester; ether or alcohol radical are further functionalized, and described initiator is preferably selected from dibenzoyl peroxide replacement or unsubstituted; 1,1-two (tert-butyl hydroperoxide)-3; 3; the 5-trimethyl-cyclohexane; 2,2-two (tert-butyl hydroperoxide) butane; 1,1-two (tert-butyl hydroperoxide) hexanaphthene; azo initiator and composition thereof; most preferably be selected from dibenzoyl peroxide; 1; 1-two (tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane; 2; 2 '-azo two (isopropyl cyanide); 2,2 '-azo two (2-methylbutyronitrile) and composition thereof.
5. according to any one method of claim 1-4, wherein temperature of reaction is 170 ℃ or lower, preferred 150 ℃ or lower, and more preferably 130 ℃ or lower, most preferably 120 ℃ or lower.
6. according to any one method of claim 1-5, wherein at least 0.5 hour, preferably during at least 1 hour in continuously or semi-continuously metered charge to the small part initiator.
7. according to any one method of claim 1-6, wherein to treat the weight of polymerization single polymerization monomer, use at least 0.01 weight % of the combination weight of whole initiators, more preferably at least 0.05 weight %, most preferably at least 0.1 weight % and preferred all 5 weight % at the most of the combination weight of initiators, more preferably 3 weight % at the most, most preferably 1 weight % at the most.
8. according to any one method of claim 1-7, wherein in the monomer polymerization degree less than 80%, preferably less than 60%,, in reaction mixture, add or the metered charge whipping agent most preferably less than 50% o'clock.
9. according to any one method of claim 1-8, wherein initiator or initiator mixture are with the form metered charge of preferably water dispersion liquid.
10. according to any one method of claim 1-9, wherein use other initiator to reduce the concentration of residual monomer.
11., be used to prepare expandable poly-styrene according to the method for claim 10.
12. styryl (being total to) polymkeric substance that can obtain by any one method of claim 1-11, after wherein this styryl (being total to) polymkeric substance is that 60 ℃ drying was also sieved in 1 hour down, residual less than 50ppm, more preferably less than 40ppm, most preferably less than the initiator of 25ppm.
13. vinylbenzene (being total to) polymkeric substance according to claim 12 is comprising that this is total to (polymkeric substance) heats with the application in the forming method of preparation foam article.
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